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Oxidative Detoxification of Sulfur-Containing Chemical Warfare Agents by Electrophilic Iodine

TitleOxidative Detoxification of Sulfur-Containing Chemical Warfare Agents by Electrophilic Iodine
Publication TypeJournal Article
Year of Publication2018
AuthorsSmolkin B., Levi N., Karton-Lifshin N., Yehezkel L., Zafrani Y., Columbus I.
JournalJ Org Chem
Volume83
Issue22
Pagination13949-13955
Date PublishedNov 16
ISBN Number0022-3263 (Linking)
Accession Number30359011
Abstract

Mild oxidation of sulfur-containing chemical warfare agents was performed in organic medium by electrophilic iodine reagents. Kinetic experiments on sulfur mustard (HD) showed rapid ( t1/2 < 3 min) and selective oxidation to the nonvesicant sulfoxide product (HD-SO) in acetonitrile or propylene carbonate solutions (9% water added) containing excess N-iodosuccinimide (NIS). Molecular iodine solutions in these solvents led to similar results as with NIS but at much slower rates ( t1/2 approximately 90 min). Higher donor number solvents, such as THF, DMF, or DMSO, showed slower rates with both iodine and NIS. The oxidation of the nerve agent O-ethyl- S-2-( N,N-diisopropylaminoethyl)methylphosphonothioate (VX) selectively to the nontoxic ethyl methylphosphonic acid product exhibited fast rates ( t1/2 = 6 min) using NIS in DMSO solution. In all other solvents tested with VX, rates were slower ( t1/2 approximately 30-70 min). Oxidation experiments under the same conditions with chloroethyl ethyl sulfide (HD simulant) and O,S-diethyl methylphosphonothioate (VX simulant) led to much faster reaction rates. These transformations are believed to proceed through electrophilic iodine attack on the sulfur moiety and display solvent dependency based on the agents' structural and chemical properties.

URLhttps://www.ncbi.nlm.nih.gov/pubmed/30359011
DOI10.1021/acs.joc.8b02306
Short TitleOxidative Detoxification of Sulfur-Containing Chemical Warfare Agents by Electrophilic Iodine

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